吲哚酚衍生物的结构——式电位关系及电氧化机理

以半经验分子轨道方法计算吲哚酚衍生物的分子结构参数.以主因子分析法和多元线性回归法研究了吲哚酚衍生物的式电位与其分子结构参数间的关系.研究发现,在所选择的19个分子结构参数中,双中心电子交换能(E

The Relation Between Formal Potential and Structure of Indophenols and Molecular Mechnism of Electrooxidation

The molecular structural parameters of indophenol and its derivatives were calculated by semi-empirical molecular orbital quantum chemical method.The relation between molecular structural parameters and formal potentials was analyzed by principal factor analysis and multiple linear regression method.It was found that the formal potential of indophenols has a good relation with two-center electron exchange energy,Eex(2),resonance energy of O-C bond,Eex(C1-O),and molecular ionization potential,Ip,among 19 moleclular structural parameters.The regression equation is E0′= 1.47× 10-3 Eex(two)-5.74× 10-2 Eex(C1-O)-1.41× 10-2 Ip with RC=0.9999 and SD=0.00424.It was confirmed by the relation between structure parameters and formal potentials,and the thermodynamic stability of its intermediate products that the H＋ ionization is prior to the electron transfer step in the oxidation mechanism.